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Synthesis 2019; 51(19): 3617-3624
DOI: 10.1055/s-0039-1690104
DOI: 10.1055/s-0039-1690104
paper
1-Nicotinoylbenzotriazole: A Convenient Tool for Site-Selective Protection of 5,7-Dihydroxycoumarins
Authors
We are grateful to the Russian Science Foundation (project #18-73-00163, synthesis of compounds 6–11) and the Ministry of Education and Science of the Russian Federation (project 4.6351.2017/8.9, synthesis of compounds 12 and 13).
Further Information
Publication History
Received: 13 March 2019
Accepted after revision: 07 June 2019
Publication Date:
26 June 2019 (online)
Abstract
1-Nicotinoylbenzotriazole (NicBt) was uncovered as an efficient protecting agent for the site-selective acylation of resorcinol-type phenolic groups with almost equal reactivity. The use of NicBt allows selective protection of the 7-OH group in 5,7-dihydroxycoumarins in one simple scalable step, while combination of the nicotinoylation with tosylation–denicotinoylation or silylation–denicotinoylation yields 5-OH-protected 5,7-dihydroxycoumarins. Furthermore, nicotinoylated 5,7-dihydroxycoumarins proved useful in a gram-scale three-step preparation of a 2,2-dimethylpyrano[2,3-f]coumarin, a key intermediate for the synthesis of calanolide A, an HIV reverse transcriptase and Mycobacterium tuberculosis inhibitor, and its active analogues.
Key words
esterification - protecting groups - phenols - acylation - natural products - total synthesisSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0039-1690104.
- Supporting Information (PDF)
- CIF File (ZIP)
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